Silicone Hydrogel Contact Lenses

ABSTRACT

Silicone hydrogel contact lenses are formed from the reaction product of a polymerizable composition comprising at least one acrylate-containing siloxane monomer, at least one hydrophilic vinyl-containing monomer, and at least one vinyl-containing cross-linking agent. The contact lenses have ophthalmically-acceptable ionoflux values and surface wettability, and can be manufactured without the use of volatile organic solvents.

This application claims the benefit under 35 U.S.C. §119(e) of prior U.S. Provisional Patent Application No. 61/447,193, filed Feb. 28, 2011, which is incorporated in its entirety by reference herein.

FIELD

The field of the invention relates to silicone hydrogel contact lenses.

BACKGROUND

Contact lenses made from silicone hydrogels are rapidly gaining popularity over contact lenses made from conventional hydrogel materials because, like conventional hydrogel lenses, they are comfortable to wear, but they have the added advantage of having higher oxygen permeability, which is believed to be healthier for the eye. However, contact lenses made from silicone hydrogels often have physical properties that make them more difficult to process during manufacturing, and typically the lenses need to be extracted in volatile organic solvents to achieve acceptable surface wettability and good dimensional stability. The use of volatile organic solvents in manufacturing presents safety and environmental concerns and adds costs to the manufacturing process.

New formulations of silicone hydrogel contact lenses that can be manufactured without the use of volatile organic solvents, and that result in dimensionally stable contact lenses having ophthalmically-acceptable surface wettabilities are desired.

Some patent documents describing silicone hydrogel contact lenses include U.S. Publ. No. 2007/0296914, U.S. Publ. No. 2007/0066706, U.S. Publ. No. 2007/0231292, U.S. Pat. No. 5,965,631, WO 2011/041523, U.S. Pat. No. 5,358,995, European Publ. No. 1870736A1, U.S. Publ. No. 2006/063852, U.S. Publ. No. 2011/0009587, and U.S. Publ. No. 2009/0234087.

SUMMARY

We have made improved silicone hydrogel contact lenses having ophthalmically acceptably wettable lens surfaces that can be manufactured without the use of volatile organic solvents. The contact lenses are prepared from a polymerizable composition comprising at least one acrylate-containing siloxane monomer, at least one hydrophilic vinyl-containing monomer, and at least one vinyl-containing cross-linking agent.

The present disclosure is directed to a silicone hydrogel contact lens comprising a polymeric lens body that is a reaction product of a polymerizable composition comprising at least one acrylate-containing siloxane monomer; at least one hydrophilic vinyl-containing monomer; and at least one vinyl-containing cross-linking agent, wherein the contact lens has an ionoflux of less than 10×10⁻³ mm²/min. In one example, the polymerizable composition has a total amount of acrylate-containing siloxane monomer of from about 2 mol. % to about 15 mol. %. In one example, the polymerizable composition has a total amount of hydrophilic vinyl-containing monomer of from about 50 mol. % to about 85 mol. %. In one example, the polymerizable composition has a total amount vinyl-containing cross-linking agent of from about 0.02 mol. % to about 0.20 mol. %. In a further example, the polymerizable composition has a molar ratio of total amount of hydrophilic vinyl-containing monomer to total amount of acrylate-containing siloxane monomer of from 5:1 to 30:1, respectively.

In one example, the hydrophilic vinyl-containing monomer can be selected from N-vinyl-N-methyl acetamide (VMA), or N-vinyl pyrrolidone (NVP), or 1,4-butanediol vinyl ether (BVE), or ethylene glycol vinyl ether (EGVE), or diethylene glycol vinyl ether (DEGVE), or any combination thereof. In a specific example, the hydrophilic vinyl-containing monomer comprises a first hydrophilic vinyl-containing monomer and a second hydrophilic vinyl-containing monomer having a polymerizable group that is different from that of the first hydrophilic monomer. In one such example, the first hydrophilic monomer can comprise or consist of a vinyl amide-containing monomer and the second hydrophilic monomer can comprise or consist of a vinyl ether-containing monomer.

In one example, the vinyl-containing cross-linking agent can be selected from divinyl ether, or divinyl sulfone, or triallyl phthalate, or triallyl isocyanurate, or diallyl phthalate, or diethyleneglycol divinyl ether, or triethyleneglycol divinyl ether, or any combination thereof.

In one example, the acrylate-containing siloxane monomer can comprises a combination of a mono-functional acrylate-containing siloxane monomer and a bi-functional acrylate-containing siloxane monomer. In a further example, the mono-functional acrylate-containing siloxane monomer has a molecular weight of less than 2,000, and the bi-functional acrylate-containing siloxane monomer has a molecular weight of at least 3,000. In yet a further example, the mono-functional acrylate-containing siloxane monomer and the bi-functional acrylate-containing siloxane monomer are present in the polymerizable composition at a molar ratio of at least 30:1, respectively.

Another aspect of the present disclosure is a method of manufacturing a silicone hydrogel contact lens, said method comprising a) preparing a polymerizable composition comprising at least one acrylate-containing siloxane monomer, at least one hydrophilic vinyl-containing monomer, and at least one vinyl-containing cross-linking agent; b) polymerizing the polymerizable composition to form a polymeric lens body; and c) contacting the polymeric lens body with a washing liquid to remove unreacted or partially reacted components from the polymeric lens body, wherein the washing liquid and any other liquid used for washing the polymeric lens body are substantially free of volatile organic solvents. In a specific example, the polymerizable composition is polymerized in a mold having non-polar molding surfaces.

DETAILED DESCRIPTION

Silicone hydrogel contact lenses are described herein that can be manufactured without the use of volatile organic solvents. The contact lenses have good manufacturing processability, are dimensionally stable, and have ophthalmically-acceptable ionoflux and surface wettability. The silicone hydrogel contact lens comprises a polymeric lens body that is the reaction product of a polymerizable composition comprising at least one acrylate-containing siloxane monomer, at least one hydrophilic vinyl-containing monomer, and at least one vinyl-containing cross-linking agent.

The following definitions for the quoted terms provided below are applicable herein unless context indicates otherwise:

A “monomer” refers to any molecule capable of reacting with other molecules that are the same or different, to form a polymer or copolymer. Thus, the term encompasses polymerizable pre-polymers and macromers, there being no size-constraint of the monomer unless indicated otherwise.

A “siloxane monomer” contains at least one Si-O group, and is typically either “mono-functional” or “multi-functional”, meaning that it has either one polymerizable group or two or more polymerizable groups, respectively. A “non-siloxane monomer” is a monomer that does not contain any Si-O groups.

An “acrylate-containing monomer” is any non-siloxane monomer that has a single polymerizable acrylate group (e.g. methyl methacrylate, acrylamide, etc.). A siloxane monomer having at least one polymerizable acrylate group is referred to herein as an “acrylate-containing siloxane monomer”.

A “vinyl-containing monomer” is any non-siloxane monomer that has a single polymerizable carbon-carbon double bond (i.e., a vinyl group) present in its molecular structure, where the carbon-carbon double bond of the vinyl group is less reactive than the carbon-carbon double bond present in an acrylate or a methacrylate polymerizable group under free radical polymerization. Thus, while a carbon-carbon double bond is present in acrylate groups and methacrylate groups, as used herein, monomers comprising a single acrylate or methacrylate polymerizable group are not considered to be vinyl-containing monomers.

A monomer is considered “hydrophilic” if at least 50 grams of the monomer are fully soluble in 1 liter of water at 20° C. (i.e., ≧5% soluble in water) as determined visibly using a standard shake flask method.

A “cross-linking agent” is any compound having a molecular weight of less than about 2,000 with two or more ethylenically unsaturated groups. Thus, a cross-linking agent can react with functional groups on two or more polymer chains so as to bridge one polymer to another. An “acrylate-containing cross-linking agent” has at least two polymerizable acrylate functional groups, and no other type of polymerizable functional group. A “vinyl-containing cross-linking agent” has at least two polymerizable vinyl groups (as defined above), and no other type of polymerizable functional group.

A “polymerizable composition” is a composition comprising polymerizable ingredients, where the composition has not yet been subjected to conditions that result in polymerization of the polymerizable ingredients.

We have discovered that the inclusion of at least one vinyl-containing cross-linking agent in a polymerizable composition comprising at least one acrylate-containing siloxane monomer and at least one non-siloxane vinyl-containing monomer can be polymerized to provide a polymeric lens body that can be processed without volatile organic solvents and result in contact lenses that have ophthalmically-acceptable ionoflux and surface wettability. References herein to ‘at least one’ of a type of ingredient refer to both a) a single ingredient, and b) a combination of two or more ingredients of the same type.

In one example, the polymerizable composition has a total amount of acrylate-containing siloxane monomer of from about 2, 3, 4, 5, or 6 molar percent (mol. %) up to about 8, 10, 12, 15, 18, or 20 mol. %; a total amount of hydrophilic vinyl-containing monomer of from about 50, 55, 60 or 65 mol. % up to about 75, 80, or 85 mol. %; and a total amount of vinyl-containing cross-linking agent of from about 0.02, 0.04, or 0.06 mol. % up to about 0.10, 0.15 or 0.20 mol. %, where molar percent values are based upon total moles of reactive ingredients in the polymerizable composition, with non-reactive ingredients, such as diluents and other non-reactive components, being excluded from the calculation. References herein to ‘a total amount’ of a particular component (i.e. a combination of two or more ingredients of the same type) in a polymerizable composition refer to the sum of the amounts of all ingredients of the same type. Further, throughout this disclosure, when a series of values is presented with a qualifier preceding the first value, the qualifier is intended to implicitly precede each value in the series unless context indicates otherwise. For example, in the above listing of molar percent ranges for the total amount of acrylate-containing siloxane monomer, it is intended that the qualifier “from about” implicitly precedes the values of 2, 3, 4, 5, and 6; and the qualifier “up to about” implicitly precedes the values of 8, 10, 12, 15, 18, and 20. Also, throughout this disclosure, when a series of values is presented with a unit of measurement following the last value of the series, the unit of measurement is intended to implicitly follow each preceding value in the series unless context indicates otherwise. For example, in the above listing of molar percent ranges for the total amount of acrylate-containing siloxane monomer, it is intended that the unit of measurement “mol. %” implicitly follows the values of 2, 3, 4, 5, 8, 10, 12, 15, and 18. Also, when a series of lower limit ranges and a series of upper limit ranges are provided, all combinations of the provided ranges are contemplated as if each combination were specifically listed. For example, in the above listing of molar percent ranges for the total amount of acrylate-containing siloxane monomer, all 30 possible molar percent ranges are contemplated (i.e. from 2 to 8 mol. %, from 2 to 10 mol. %, from 2 to 15 mol. % . . . from 6 to 15 mol. %, from 6 to 18 mol. %, and from 6 to 20 mol. %). Also, throughout this disclosure a reference to “an example” or “a specific example” or similar phrase, is intended to introduce a feature or features of the contact lens, polymerizable composition, or method of manufacture (depending on context) that can be combined with any combination of previously-described or subsequently-described examples (i.e. features), unless a particular combination of features is mutually exclusive, or if context indicates otherwise.

Examples of vinyl-containing cross-linking agents that can be used in the polymerizable compositions disclosed herein include, without limitation, divinyl ethers, or divinyl sulfones, or triallyl isocyanurates, and any combination thereof. Exemplary divinyl ethers include diethyleneglycol divinyl ether, or triethyleneglycol divinyl, or 1,4-butanediol divinyl ether, or 1,4-cyclohexanedimethanol divinyl ether, or any combination thereof. Other cross-linking agents suitable for use in silicone hydrogel polymerizable compositions are known in the field (see e.g. the patent publications listed in the Background section). Typically, the vinyl-containing cross-linking agent can have two or three polymerizable vinyl groups. The vinyl-containing cross-linking agents, as well as the acrylate-containing cross-linking agents described further below, typically can have a molecular weight of less than 1500, 1000, 500, or 250, wherein the molecular weight units are given in Daltons, here and throughout this disclosure. In a specific example, the polymerizable composition has a ratio of polymerizable vinyl groups from the total amount of hydrophilic vinyl-containing monomer (i.e. one polymerizable vinyl group per molecule) to polymerizable vinyl groups from the total amount of vinyl-containing cross-linking agent (i.e. at least two polymerizable vinyl groups per molecule) of about 50:1, or 100:1 or 200:1 up to about 800:1, or 1000:1, or 1200:1.

Examples of hydrophilic vinyl-containing monomers that can be used in the polymerizable formulations described herein include hydrophilic monomers having a single vinyl ether, or vinyl ester, or allyl ester, or vinyl amide polymerizable group. Exemplary hydrophilic vinyl-containing monomers include N-vinyl-N-methyl acetamide (VMA), N-vinyl pyrrolidone (NVP), 1,4-butanediol vinyl ether (BVE), ethylene glycol vinyl ether (EGVE), diethylene glycol vinyl ether (DEGVE), and combinations thereof. Other suitable hydrophilic vinyl-containing monomers that can be used in the polymerizable compositions are described, for example, in the patent publications referenced in the Background section above, which are incorporated herein by reference in their entireties.

In a specific example, the at least one hydrophilic vinyl-containing monomer can comprise or consist of a first hydrophilic vinyl-containing monomer and a second hydrophilic vinyl-containing monomer having a polymerizable functional group that is different from that of the first hydrophilic monomer. In one example, this can increase wettability of the contact lens compared to a formulation that comprises a single hydrophilic vinyl-containing monomer, but is otherwise identical. In one such example, the first hydrophilic monomer can be a “vinyl amide-containing monomer”, which, as used herein, refers to a monomer that contains an N-vinyl polymerizable group, and no other polymerizable group, where N designates nitrogen. The second hydrophilic monomer can be a “vinyl ether-containing monomer”, which, as used herein, refers to a monomer that contains an O-vinyl polymerizable group, and no other polymerizable group, where O designates oxygen. For example, the first hydrophilic monomer can be selected from N-vinyl-N-methyl acetamide (VMA) or N-vinyl pyrrolidone (NVP), or N-vinyl formamide, or N-vinyl acetamide, or N-vinyl-N-ethyl acetamide, or N-vinyl isopropylamide, or N-vinyl caprolactam, or N-vinyl-N-ethyl formamide, or any combination thereof; and the second hydrophilic monomer can be selected from 1,4-butanediol vinyl ether (BVE), or ethylene glycol vinyl ether (EGVE), or diethylene glycol vinyl ether (DEGVE), or 1,4-cyclohexanedimethanol vinyl ether (CHDMVE), or a poly(ethylene glycol) vinyl ether having from 4 to 10 ethylene glycol units, or a poly(ethylene glycol) vinyl ether having more than 10 ethylene glycol units, or any combination thereof. In such an example, the polymerizable composition can have a molar ratio of the total amount of vinyl amide-containing monomer to the total amount of vinyl ether-containing monomer of from about 2:1, 3:1, 4:1, or 5:1 up to about 15:1, 20:1, 25:1, or 30:1 respectively. Additionally, the polymerizable composition can comprise from about 50, 55, or 60 mol. % to about 70, 75, 80, or 85 mol. % of the vinyl amide-containing monomer, and from about 2, 4, or 6 mol. % to about 10, 15, 20, or 25 mol. % of the vinyl ether-containing monomer.

In various examples where more than one hydrophilic vinyl-containing monomer is included in the polymerizable composition, at least 50%, 60%, 70% or 80% by weight of the hydrophilic vinyl-containing monomer has a solubility in water of≧10%, 15% or 20%. In a specific example, 100% of the hydrophilic vinyl-containing monomer in the polymerizable composition has a solubility in water of≧10%, 15%, or 20%. The hydrophilic vinyl-containing monomer typically has a molecular weight of about 75 to about 500, and more typically about 75 to 250.

Acrylate-containing siloxane monomers that can be used in the polymerizable compositions described herein are well-known in the field, such as those referenced in the patent publications cited in the Background section above. The acrylate-containing siloxane monomer may be mono-functional, bi-functional, or comprise a combination of mono- and bi-functional acrylate-containing siloxane monomers. In examples where the acrylate-containing siloxane monomer consists of one or more mono-functional acrylate-containing siloxane monomers (i.e. it does not contain any multi-functional acrylate-containing siloxane monomers), the polymerizable composition will typically further comprise an acrylate-containing cross-linking agent, described further below. In a specific example, the acrylate-containing siloxane monomer has one or more polymerizable methacrylate groups. Various non-limiting examples of suitable acrylate-containing siloxane monomers include 3-[tris(trimethylsiloxy)silyl]propyl methacrylate (“TRIS”), 3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane (“SiGMA”), methyldi(trimethylsiloxy)sylylpropylglycerolethyl methacrylate (“SiGEMA”), and monomethacryloxypropyl functional polydimethylsiloxanes such as MCR-M07 and MCS-M11, all available from Gelest (Morrisville, Pa., USA).

In one example, the acrylate-containing siloxane monomer may comprise a monomer represented by formula (I),

where m is an integer from 3 to 10, n is an integer from 0 to 10, R¹ is an alkyl group having 1 to 4 carbon atoms, R² is hydrogen or a methyl group, and R³ is hydrogen or a methyl group. In a further specific example, the acrylate-containing siloxane monomer is represented by formula I wherein R¹ is a butyl group, R² is hydrogen, R³ is a methyl group, m is 4, and n is 1. This particular siloxane monomer is designated “Si-1” in the Examples section below. Methods of making siloxane monomers represented by formula (I) are described in U.S. Publ. no. 20090299022, incorporated herein by reference.

Another exemplary acrylate-containing siloxane monomer is represented by formula (II),

wherein R₁ is selected from either hydrogen or a methyl group; R₂ is selected from either hydrogen or a C₁₋₄ hydrocarbon group; m represents an integer of from 0 to 10; n represents an integer of from 4 up to about 15, 25, or 100; a and b represent integers of 1 or more; a+b is equal to 20-500; b/(a+) is equal to 0.01-0.22; and the configuration of siloxane units includes a random configuration. In a more specific example, the acrylate-containing siloxane monomer is represented by formula II wherein R₁ and R₂ are methyl groups, m is 0, n represents an integer from about 5 to about 10, a represents an integer of from about 70 to about 90, and b represent an integer of from 1 to about 10; this siloxane monomer is designated “Si-2” in the Examples section below and has a molecular weight of about 8,000 to about 10,000. Methods of making compounds of formula II are described in U.S. Publication no. 2009/0234089, incorporated herein by reference.

Yet another exemplary acrylate-containing siloxane monomer is represented by formula (III),

where n is an integer from about 10 to 15. Siloxane monomers of formula III and other suitable monomers are described in U.S. Pat. No. 6,867,245 and U.S. Pat. No. 6,310,169, both incorporated herein by reference.

Other suitable acrylate-containing siloxane monomers are represented by formula (IV):

wherein R³ is selected from either hydrogen or a methyl group, m represents an integer from 0 to 10, and n represents an integer from 1 to 500. In a specific example, the acrylate-containing siloxane monomer is a methacryloxypropyl-terminated polydimethylsiloxane represented by formula III where R³ is a methyl group, m is 0, and n is an integer from 40 to 60. This monomer is available from Gelest (Morrisville, Pa., USA) and is referred to as “DMS-R18” from the manufacturer and as “Si-3” in the Examples below. Additional suitable methacryloxypropyl-terminated polydimethylsiloxanes include DMS-R22 and DMS-R31, also available from Gelest.

Yet another suitable acrylate-containing siloxane monomer is represented by formula (V),

wherein n is an integer of about 100 to 150, m and p are both integers of about 5 to 10, and h is an integer of about 2 to 8. Methods of making compounds of formula V are described in U.S. Pat. No. 6,867,245, incorporated herein by reference. Additional acrylate-containing siloxane monomers that can be used in the polymerizable composition described herein are known in the field (see e.g. U.S. Pat. No. 7,572,841, U.S. Publ. No. 2006/0063852, and U.S. Pat. No. 5,998,498, each incorporated herein by reference).

In one example, the acrylate-containing siloxane monomer may comprise a combination of a mono-functional acrylate-containing siloxane monomer and a bi-functional acrylate-containing siloxane monomer. In this example, the bi-functional acrylate-containing siloxane monomer may be present in the polymerizable composition in amounts of from about 0.04, 0.06, 0.08, or 0.10 mol. % and up to about 0.20, 0.25, 0.30, or 0.35 mol. %; and the mono-functional acrylate-containing siloxane monomer may be present in amounts of from about 2, 3, 4 or 5 mol. % up to about 8, 10, 12, 15, or 18 mol. %. In one such example, the mono-functional acrylate-containing siloxane monomer has a molecular weight of less than 2,000, 1,500, 1,000, or 750, and the bi-functional acrylate-containing siloxane monomer has a molecular weight of at least 3,000, 3,500, 4,000, 4,500, 5,000, 6,000, 7,000, or 8,000. In the case of polyorganosiloxane prepolymers, such as those represented by Formulas III, IV, and V above, and other polydisperse monomers, the term “molecular weight” as used herein, refers to the absolute number average molecular weight (in units of Daltons) of the monomer as determined by ¹H NMR end-group analysis. In a specific example, the mono-functional acrylate-containing siloxane monomer has a molecular weight of from about 250 to about 1000, and the bi-functional acrylate-containing siloxane monomer has a molecular weight of from about 5,000 to about 16,000. In a further specific example, the mono-functional acrylate-containing siloxane monomer has a molecular weight of from about 500 to about 1000, and the bi-functional acrylate-containing siloxane monomer has a molecular weight of from about 5,000 to about 12,000.

In the above-described example wherein the acrylate-containing siloxane monomer comprises a combination of a mono-functional acrylate-containing siloxane monomer and a bi-functional acrylate-containing siloxane monomer, the mono-functional acrylate-containing siloxane monomer and bi-functional acrylate-containing siloxane monomer may be present in the polymerizable composition at a molar ratio of at least 20:1, 30:1, 40:1, 50:1, 75:1 or 100:1, and optionally up to about 150:1, 175:1, 200:1, 225:1 or 250:1, respectively. In a specific example, the molar ratio of the mono-functional acrylate-containing siloxane monomer to bi-functional acrylate-containing siloxane monomer is from 30:1 up to 150:1, wherein the mono-functional acrylate-containing siloxane monomer has a molecular weight of from about 500 to about 1000, and the bi-functional acrylate-containing siloxane monomer has a molecular weight of from about 5,000 to about 12,000.

In one example, the polymerizable composition may further comprise a non-siloxane acrylate-containing monomer to further enhance mechanical strength and/or stiffness of the lens, or confer other desired properties. When present, the total amount of non-siloxane acrylate-containing monomer in the polymerizable composition is typically from about 12, 14, 16, or 18 mol. % and up to about 20, 25, or 30 mol. %. In a specific example, the non-siloxane acrylate-containing monomer has a polymerizable methacrylate group. Numerous suitable non-siloxane acrylate-containing monomers are known in the field. Exemplary acrylate-containing monomers include methyl methacrylate (MMA), 2-hydroxybutyl methacrylate (HOB), tert butyl methacrylate (tBMA), N,N-dimethylacrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA), ethoxyethyl methacrylamide (EOEMA), ethylene glycol methyl ether methacrylate (EGMA), isobornyl methacrylate (IBM), and combinations thereof.

In one example, the polymerizable composition may additionally comprise an acrylate-containing cross-linking agent. When present, the total amount of acrylate-containing cross-linking agent in the polymerizable composition is typically from about 0.20, 0.25, 0.30, or 0.35 mol. % up to about 0.50, 0.60, 0.70, 0.80, or 1.0 mol. %. In one such example, the total amount of acrylate-containing cross-linking agent and the total amount of vinyl-containing cross-linking agent are at a molar ratio of at least 3:2, 2:1, 3:1, or 4:1, and optionally up to about 16:1, 14:1, 12:1, or 10:1, respectively. In certain examples the acrylate-containing cross-linking agent is free of siloxane moieties, i.e. it is a non-siloxane cross-linking agent. Examples of acrylate-containing cross-linking agents that can be used in the polymerizable compositions disclosed herein, include, without limitation, lower alkylene glycol di(meth)acrylate, poly(lower alkylene) glycol di(meth)acrylate, lower alkylene di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, bisphenol A di(meth)acrylate, methylenebis(meth)acrylamide, and 1,3-Bis(3-methacryloxypropyl)tetramethyldisiloxane. In a specific example, the vinyl-containing cross-linking agent is a divinyl ether such as triethyleneglycol divinyl ether (TEGDVE) or diethyleneglycol divinyl ether (DEGDVE), and the acrylate-containing cross-linking agent is a lower alkylene glycol dimethacrylate such as triethylene glycol dimethacrylate (TEGDMA) or ethylene glycol dimethacrylate (EDGMA). In other examples, there is no non-siloxane acrylate-containing cross-linking agent in the polymerizable composition, and the presence of a bi-functional acrylate-containing siloxane monomer in the polymerizable composition provides an acrylate cross-linking function. In exemplary polymerizable compositions, the total amount of all cross-linkable ingredients in the polymerizable composition (i.e. any reactive ingredient having more than one polymerizable group, such as a bi-functional siloxane, a vinyl-containing cross-linking agent, etc.) is from about 0.2, 0.4, or 0.6 mol. % up to about 0.8, 1.0, 1.2, or 1.5 mol. %.

The polymerizable compositions can also be described in terms of the percentage by weight (wt. %) of each reactive component in the polymerizable composition, and wt. % ratios of various reactive components, wherein the weight percentages are based on total weight of reactive components of the composition relative to the total weight of all reactive components. For example, the polymerizable composition may have a total amount of acrylate-containing siloxane monomer of from about 20 wt. % or 30 wt. % up to about 50 wt. % or 60 wt. %; a total amount of hydrophilic vinyl-containing monomer of from about 30 wt. %, or 40 wt. % up to about 50 wt. % or 60 wt. %; and a total amount of vinyl-containing cross-linking agent of from about 0.02 wt. % or 0.05 wt. % up to about 0.5 wt. % or 1.0 wt. %. The polymerizable composition may additionally have a total amount of an acrylate-containing cross-linking agent of from about 0.05 wt. % to about 4 wt. %. In one example, the polymerizable composition may further comprise from about 5 wt. % or 10 wt. % up to about 20 wt. % or 25 wt. % of an acrylate-containing monomer. In a further specific example, the acrylate-containing siloxane monomer component of the polymerizable composition comprises a combination of at least one mono-functional acrylate-containing siloxane monomer having a molecular weight of less than 2,000, and at least one bi-functional acrylate-containing siloxane monomer having a molecular weight of at least 3,000 at a wt. % ratio of at least 2:1, respectively, wherein the total amount of the mono- and bi-functional acrylate-containing siloxane monomers comprise about 25 to 50 wt. %, or 30 to 45 wt. % of the composition. These wt. % examples of the polymerizable composition may be combined with any of the above-described molar ratio and/or molar percentage examples.

Polymerizable compositions described herein result in contact lenses that have ophthalmically acceptably wettable lens surfaces without the inclusion of a high molecular weight hydrophilic polymer (i.e. a preformed polymer) in the polymerizable composition. In a particular example, the polymerizable composition is substantially free of a hydrophilic polymer. As used herein, “substantially free” means none or an inconsequential amount, i.e. an amount that has no measurable affect on the physical properties of the lens. However, such hydrophilic polymers may be included in the polymerizable composition, if desired. Examples of such hydrophilic polymers include polyamides, polylactams (especially polyvinylpyrrolidone), polyimides, polylactones, and polydextrans, having molecular weights of at least 50,000, and are described in U.S. Pat. No. 6,367,929, incorporated herein by reference. Accordingly, in another example the polymerizable composition additionally comprises a hydrophilic polymer in an amount that increases the wettability of the contact lens relative to a contact lens that lacks the hydrophilic polymer but is otherwise identical.

As will be appreciated by those skilled in the art, the polymerizable composition will typically comprise non-polymerizable ingredients, in addition to the polymerizable ingredients, that are conventionally used in contact lens formulations. For example, the polymerizable composition will typically include a polymerization initiator, a UV absorbing agent, and a tinting agent. Additional ingredients may also be included such as an organic diluent, an oxygen scavenger, or a chain transfer agent. Non-limiting examples of these and additional ingredients that may be included in the polymerizable composition are provided in U.S. Publication No. 2007/0296914, and below.

Contact lenses can be made from the polymerizable compositions described herein using curing and other processing methods known in the field, such as cast molding, spin casting, injection molding, forming a polymerized rod that is subsequently lathed, etc. In a specific example, the polymerizable composition is cast molded between molds formed of a thermoplastic polymer. The thermoplastic polymer is typically a non-polar material, such as polypropylene, but polar mold materials are also used in the field. Briefly, a first mold member defining the front surface of the contact lens, referred to as a “female mold member”, is filled with an amount of the polymerizable composition sufficient to form a single polymeric lens body. A second mold member defining the back (i.e. eye-contacting) surface of the contact lens, referred to as the “male mold member”, is coupled to the female mold member to form a mold assembly having a lens-shaped cavity with the amount of polymerizable composition therebetween.

The polymerizable composition within the contact lens mold assembly is polymerized using any suitable curing method. Typically, the polymerizable composition is exposed to polymerizing amounts of heat or ultraviolet light (UV). In the case of UV-curing, also referred to as photopolymerization, the polymerizable composition typically comprises a photoinitiator such as benzoin methyl ether, 1 -hydroxycyclohexylphenyl ketone, Darocur or Irgacur (available from Ciba Specialty Chemicals). Photopolymerization methods for contact lenses are described in U.S. Pat. No. 5,760,100. In the case of heat-curing, also referred to as thermal curing, the polymerizable composition typically comprises a thermal initiator. Exemplary thermal initiators include 2,2′-azobis(2,4-dimethylpentanenitrile) (VAZO-52), 2,2′-Azobis(2-methylpropanenitrile) (VAZO-64), and 1,1 -azo bis(cyanocyclohexane) (VAZO-88). In an exemplary thermal curing method that can be used to polymerize polymerizable compositions described herein, the mold assemblies are subjected to a first curing temperature of from about 50 to 65° C., which is maintained for about 15 to 45 minutes, and then the temperature is increased to a second temperature of at least about 70° C. In one such example, the second curing temperature can be from about 70 to 85° C. and can be maintained for about 15 to 45 minutes, then the temperature can be increased again to at least about 90° C., and can be maintained until polymerization is substantially complete, typically at least about 15 minutes. Additional thermal polymerization methods for contact lenses are described in U.S. Publ. No. 2007/0296914 and U.S. Pat. No. 7,854,866, incorporated herein by reference.

In a specific example, during the polymerizing step, less than 50% of polymerizable vinyl groups from the polymerizable composition have polymerized by the time 80% of polymerizable acrylate groups from the polymerizable composition have polymerized. In a further example, less than 50% of polymerizable vinyl groups from the polymerizable composition have polymerized by the time 95% of polymerizable acrylate groups from the polymerizable composition have polymerized. A curing system with Fourier-transform infrared (FT-IR) and near-infrared (NIR) spectroscopy monitoring capability can be used to monitor the extent of conversion (i.e. polymerization) of the polymerizable vinyl groups and polymerizable acrylate groups of a polymerizable composition.

At the completion of curing, the polymerized material between the mold members of the mold assembly has the shape of a contact lens, and is referred to herein as a “polymeric lens body”. The male and female mold members are demolded, i.e. separated, and the polymeric lens body is removed, i.e. delensed, from the mold member to which it is adhered. These processes are referred to as demolding and delensing, respectively, and a variety of such methods are known to those of ordinary skill in the field. In some methods, the demolding and delensing processes can comprise a single process step, such as when the molds are separated using a liquid which also removes the polymeric lens body from the mold. In other methods, such as when a dry-demolding process is used, the polymeric lens body typically remains on one of the mold members and is delensed in a subsequent process step. Delensing can also be a wet or dry process. In one example, delensing is carried out by a “float off” method in which the mold member to which a polymeric lens body is adhered is immersed in water. The water may optionally be heated (e.g. up to about 100° C.). Typically, the polymeric lens bodies float off of the mold members in about ten minutes. Dry delensing can be carried out manually, for example using tweezers to remove the polymeric lens bodies from the mold member, or they can be removed using an automated mechanical process, such as described in U.S. Pat. No. 7,811,483. Additional demolding and delensing methods for silicone hydrogel contact lenses are described in U.S. Publ No. 2007/0035049.

After delensing, the polymeric lens body is washed to remove unreacted or partially reacted ingredients from the polymeric lens body and to hydrate the polymeric lens body. In a specific example, the polymeric lens body is washed in a washing liquid free of volatile organic solvents (e.g. methanol, ethanol, chloroform, etc.), and all liquids used to wash the polymeric lens body are free of volatile organic solvents. This type of washing may also be referred to herein as “organic solvent-free extraction” where “organic solvent” refers to volatile organic solvents. For example, a washing step that uses aqueous solutions of surfactants such as Tween 80, without any volatile organic solvents, is considered to be a volatile organic solvent-free extraction. In a further example, the polymeric lens body is not contacted by any volatile organic solvents during the manufacturing process (i.e. from the time curing of the polymeric lens body is complete until the time it is sealed in its final packaging). While the polymerizable compositions described herein can be used to make polymeric lenses bodies that can be washed without the use of volatile organic solvents, if desired, they can also be washed with organic solvents. Thus, washing steps can include contacting the polymeric lens body with a volatile organic solvent, such as a lower alcohol (e.g. methanol, ethanol, etc.), contacting the polymeric lens body with aqueous liquids that may or may not contain a volatile organic solvents, solutes, or combinations thereof. Exemplary washing methods are described in U.S. Pat Publ No. 2007/0296914 and in Example 1 below.

The good wettability of the contact lenses achieved from the polymerizable compositions described herein avoids the need for post-polymerization surface modification of the polymeric lens body to impart wettability. One example of a post-polymerization surface modification used to impart wettability is surface plasma treatment (see e.g. U.S. Pat. No. 4,143,949). Another example of a post-polymerization modification to impart wettability is the coating of hydrophilic polymers onto the surface of the polymeric lens body such as by a layer-by-layer technique (see e.g. U.S. Pat. No. 7,582,327), or by the addition of a hydrophilic polymer into the packaging solution (see e.g. U.S. Pat. No. 7,841,716). Accordingly, in a specific example, the method of making the contact lens is free of a post-polymerization surface modification. For example, the method may not include a plasma surface modification of the polymeric lens body and/or a hydrophilic polymer may not be coated onto the polymeric lens body and/or a hydrophilic polymer may not be added to the packaging solution that is placed into the contact lens package.

After washing, and any optional surface modifications, the hydrated polymeric lens body is typically placed into a blister package, glass vial, or other appropriate container, all referred to herein as “packages.” A packaging solution is also added to the container, which is typically a buffered saline solution such as phosphate- or borate-buffered saline. The packaging solution may optionally contain additional ingredients such as a comfort agent, a hydrophilic polymer, a surfactant or other additive that prevents the polymeric lens body from sticking to the container, etc. The package is sealed, and the sealed polymeric lens body is sterilized by sterilizing amounts of radiation, including heat or steam, such as by autoclaving, gamma radiation, e-beam radiation, ultraviolet radiation, etc. The final product is a sterile, packaged ophthalmically-acceptable contact lens.

Typically, contact lenses that have been processed using organic solvent-free extraction will have a “wet extractable component”. In specific examples, the wet extractable component of the final contact lens product constitutes about 2 to about 8% of the dry weight of the lens, and usually about 3 to about 6% of the dry weight of the contact lens. The percentage of the wet extractable component in a contact lens is determined using a Sohxlet extraction process as follows: Five fully-hydrated, sterilized contact lenses from a single lot are removed from their packages and excess packaging solution is removed from the lenses with a paper towel. The lenses are dried overnight in an 80° C. vacuum oven, then each dried lens is weighed to get the dry weight of the lens (W1). Each lens is then placed in a perforated, stackable Teflon thimble, and the thimbles are stacked to form an extraction column with an empty thimble placed at the top of the column. The extraction column is placed into a small Sohxlet extractor (VWR 80068-164) and the extractor is attached to a condenser (VWR 80068-1580) and a 125 ml round bottom flask (VWR-80068-704) containing about 70-80 ml methanol. Water is circulated around the condenser and the methanol is heated until it gently bubbles. The lenses are extracted for 4 hours from the time condensed methanol first begins to drop. The methanol-extracted lenses are removed from the thimbles and dried overnight at 80° C. in a vacuum oven. Each lens is weighed to obtain the dry weight of the extracted lens (W2), and the following calculation is made for each lens: [(W1-W2)/W1]*100. The average of the five values is taken to be the percentage of wet extractable for each lens of the lot of lenses tested.

The contact lenses described herein are “ophthalmically-acceptable” meaning that the lenses have ophthalmically acceptably wettable lens surfaces and ionoflux values such that the lenses typically do not cause or are not associated with significant corneal swelling, corneal dehydration (“dry eye”), superior epithelial arcuate lesions (“SEALs”), or other significant discomfort. Determining whether a contact lens is ophthalmically acceptable can be achieved using conventional clinical methods, such as those performed by an eye care practitioner, and as understood by persons of ordinary skill in the art.

In any of the above-described examples, the contact lens may be characterized by one or more of the following properties: ionoflux, contact angle, oxygen permeability, tensile modulus, equilibrium water content, and % energy loss, as detailed in the following seven paragraphs.

In any of the above-described examples, the contact lens may have an ionoflux of less than about 10×10⁻³ mm²/min, 9×10⁻³ mm²/min, 8×10⁻³ mm²/min, 7×10⁻³ mm²/min, 6×10⁻³ mm²/min, 5×10⁻³ mm²/min, or 4×10⁻³ mm²/min as measured using the “Ionoflux Technique” described in U.S. Pat. No. 5,849,811, incorporated by reference herein, or an equivalent method such as the following method that was used to determine the ionoflux values provided in the Examples below. A hydrated lens is placed in 40 ml deionized water for 10 minutes. The lens is then placed in a lens-retaining device, between male and female portions. The male and female portions include flexible sealing rings which are positioned between the lens and the respective male or female portion. The lens-retaining device is then placed in a threaded lid. The lid is screwed onto a glass tube to define a donor chamber. The donor chamber is filled with 16 ml of 0.1 molar NaCl solution. A 100 ml beaker, used as a receiving chamber, is filled with 80 ml of deionized water. Leads of a conductivity meter and a stir bar are immersed in the deionized water of the receiving chamber. The receiving chamber is placed in a 250 ml beaker jacket that was filled with about 50 ml deionized water and connected to a water bath with temperature control set to achieve a temperature of about 35° C. in the receiving chamber. Finally, the donor chamber is immersed in the receiving chamber so that the NaCl solution inside the donor chamber is level with the water inside the receiving chamber. Once the temperature inside the receiving chamber reaches 35° C., conductivity is recorded for 10 minutes. The conductivity versus time data in each of the examples below was substantially linear.

In any of the above-described examples, the contact lens may have a contact angle of less than about 80°, 70°, or 60° , where the contact angle is the dynamic advancing contact angle as determined using a captive bubble method using a DSA 100 Drop Shape Analysis System from Krüss as described in Maldonado-Codina, C. and Morgan, P. B. (2007), In vitro water wettability of silicone hydrogel contact lenses determined using the sessile drop and captive bubble techniques. Journal of Biomedical Materials Research Part A, 83A: 496-502.

In any of the above-described examples, the oxygen permeability of the contact lens (Dk) may be at least 55 barrers, or at least 60 barrers. Dk values can be determined using standard methods in the industry, such as by using an Ox-Tran model oxygen transmission rate test system available from Mocon, Inc (Minneapolis, Minn.). The Dk values provided in the Examples below were determined using the method described by Chhabra et al. (2007), A single-lens polarographic measurement of oxygen permeability (Dk) for hypertransmissible soft contact lenses. Biomaterials 28: 4331-4342.

In any of the above described examples, the contact lens may have a tensile modulus (i.e. Young's modulus) of about 0.2 MPa, 0.3 MPa, or 0.4 MPa, up to about 0.7 MPa, 0.8 MPa, or 0.9 MPa as measured by an ANSI Z80.20 standard using an Instron Model 3342 or Model 3343 mechanical testing system, or equivalent method. The modulus, elongation, and tensile strength values reported herein were determined using an Instron Model 3342 or 3343 mechanical testing system (Instron Corporation, Norwood, Mass., USA) and Bluehill Materials Testing Software, using a custom built rectangular contact lens cutting die with 4 mm spacing to prepare the rectangular sample strip. The modulus was determined inside a chamber having a relative humidity of least 70%. A lens was soaked in phosphate buffered solution (PBS) for at least 10 minutes prior to testing. While holding the lens concave side up, a central strip of the lens was cut using the cutting die. The thickness of the strip was determined using a calibrated gauge (Rehder electronic thickness gauge, Rehder Development Company, Castro Valley, Calif., USA). Using tweezers, the strip was loaded into the grips of the calibrated Instron apparatus, with the strip fitting over at least 75% of the grip surface of each grip. A test method designed to determine the maximum load (N), the tensile strength (MPa), the strain at maximum load (% elongation) and the mean and standard deviation of the tensile modulus (MPa) was run, and the results were recorded.

In any of the above-described examples, the contact lens may have an equilibrium water content (EWC) of greater than about 30 wt. %, 40 wt. % or 50 wt. % and up to about 60 wt. % or 70 wt. %. To measure EWC, excess surface water is wiped off of the lens and the lens is weighed to obtain the hydrated weight. The lens is dried in an oven at 80° C. under a vacuum, and weighed. The weight difference is determined by subtracting the weight of the dry lens from the weight of the hydrated lens. The wt. % EWC of the lens is =(weight difference/hydrated weight)×100. In a specific example, the contact angle is ≦70 ° and the equilibrium water content is at least about 40 wt. %.

The contact lenses described herein are considered “dimensionally stable” if they are from a batch (i.e. lot) of contact lenses that exhibit an average dimensional stability variance of ≦±3.0% (i.e. less than or equal to plus or minus three percent) as determined by the following method. The chord diameters of twenty lenses from a single lot are measured, and the average “original” diameter is obtained. Concurrently, twenty unopened packages of lenses from the same lot are placed in an incubator set at 55° C. The lenses are kept at this elevated temperature storage condition for three months to approximate a two-year shelf life at 25° C. At the end of three months the packaged lenses are brought to room temperature, removed from their packaging, and measured to obtain the average “final” diameter. The dimensional stability variance is calculated by the equation: (Diameter _(Final)-Diameter _(original)/Diameter _(original)) ×100. In some examples, the dimensional stability variance is ≦±2.5% or ≦±2.0%. In other examples, the lenses have a dimensional stability variance of ≦±3.0% as determined using the above-described method except that the incubator is set at 65° C. This elevated temperature storage condition is considered to approximate a four-year shelf life at 25° C.

In any of the above described examples, the contact lens may have a percent energy loss of at least about 25, 27, or 30 up to about 37, 40, or 45 as determined using a test method in accordance with ANSI Z80.20. The energy loss values reported herein were determined using an Instron Model 3343 (Instron Corporation, Norwood, Mass., USA) mechanical testing system, with a 10N force transducer (Instron model no. 2519-101) and Bluehill Materials Testing Software including a TestProfiler module. Briefly, the energy loss was determined inside a chamber having a relative humidity of least 70%. A lens was soaked in phosphate buffered solution (PBS) for at least 10 minutes prior to testing. Using tweezers, the lens was loaded into the grips of the calibrated Instron apparatus, with the lens loaded vertically between the grips as symmetrically as possible and fitting over at least 75% of the grip surface of each grip. A test designed to determine the energy required to stretch the lens to 100% strain and then return it to 0% strain at a rate of 50 mm/minute was then run on the lens. The test was conducted only once on a single lens. Once the test was finished energy loss was calculated: Lost Energy (%)=(Energy to 100% strain-Energy to return to 0% strain)/Energy to 100% strain×100%.

As is evident from the disclosure of the application as a whole, including the claim structure and the specific examples, the exemplary components of the polymerizable composition disclosed herein are typically combined in embodiments of the invention. For example, the person skilled in the art would recognise that the polymerizable composition of the invention advantageously includes the exemplary acrylate-containing siloxane monomers disclosed herein in combination with the exemplary hydrophilic vinyl-containing monomers disclosed herein and/or in combination with the exemplary vinyl-containing cross-linking agents disclosed herein.

Thus, the acrylate-containing siloxane monomers disclosed in paragraphs [027]-[032] above are present in the polymerizable compositions of the invention in combination with any of the hydrophilic vinyl-containing monomers disclosed in paragraph [024], or combinations of hydrophilic vinyl-containing monomers disclosed in paragraph [025]. For example, the acrylate-containing siloxane monomers of formula (I) may optionally be used in combination with any one of the hydrophilic vinyl-containing monomers disclosed in paragraph [024], especially in combination with VMA, NVP, BVE, EGVE, or DEGVE.

Similarly, the acrylate-containing siloxane monomers disclosed in paragraphs [027]-[032] above are present in the polymerizable compositions of the invention in combination with any of the vinyl-containing cross-linking agents disclosed in paragraph [023]. For example, the acrylate-containing siloxane monomers of formula (I) may optionally be used in combination with any one of the vinyl-containing cross-linking agents disclosed in paragraph [023], especially in combination with TEGDVE or DEGDVE.

Similarly, the hydrophilic vinyl-containing monomers disclosed in paragraph [024], or combinations of hydrophilic vinyl-containing monomers disclosed in paragraph [025] are, advantageously, present in the polymerizable compositions of the invention in combination with any of the vinyl-containing cross-linking agents disclosed in paragraphs [023]. For example, VMA, NVP, BVE, EGVE, or DEGVE may optionally be used in combination with any of the vinyl-containing cross-linking agents disclosed in paragraphs [023], especially in combination with TEGDVE or DEGDVE.

Furthermore, the acrylate-containing siloxane monomers disclosed in paragraphs [027]-[032] above are, advantageously, present in the polymerizable compositions of the invention in combination with any of the hydrophilic vinyl-containing monomers disclosed in paragraph [024], or combinations of hydrophilic vinyl-containing monomers disclosed in paragraph [025], and any of the vinyl-containing cross-linking agents disclosed in paragraphs [023]. Thus, the polymerizable compositions of the invention may optionally include a combination of one or more of the acrylate-containing siloxane monomers of formula (I), together with both (i) a hydrophilic vinyl-containing monomer (such as VMA, NVP, BVE, EGVE, or DEGVE) and (ii) a vinyl-containing cross-linking agent (such as TEGDVE or DEGDVE).

As demonstrated by the specific examples, it has been found that a combinations of the preferred acrylate-containing siloxane monomers, hydrophilic vinyl-containing monomers, and/or vinyl-containing cross-linking agents of the invention provide contact lenses of the invention with low ionoflux and/or other advantageous properties.

EXAMPLES

The following Examples illustrate certain aspects and advantages of the present invention, which should be understood not to be limited thereby. Example 1 describes contact lens processing methods, and Examples 2-12 show exemplary polymerizable compositions that were used to make contact lenses using the methods described in Example 1. The polymerizable compositions had good processability resulting in defect- and distortion-free contact lenses. The contact lenses produced were optically clear, meaning that light transmittance between 381nm to 780 nm was at least 97% (measured in accordance with ISO 18369). Additional physical properties of the lenses are provided in the examples below. Table 1 shows the abbreviation used for each ingredient as well as its molecular weight, which was used to calculate the molar ratios shown in each example. The molar ratios were determined by dividing the unit amount of an ingredient by its molecular weight to obtain the relative molar amount of the ingredient in the polymerizable composition, and comparing that value to the molar amount of another ingredient in the composition. The molar ratios compared are designated A-C in each example as follows: A. hydrophilic vinyl-containing monomer to acrylate-containing siloxane monomer; B. monofunctional acrylate-containing siloxane monomer to bifunctional acrylate-containing siloxane monomer; and C. vinyl amide-containing monomer to vinyl ether-containing monomer. Additionally, the ratio of polymerizable vinyl groups from the hydrophilic vinyl-containing monomers (i.e. one per molecule) respective to the polymerizable vinyl groups from the vinyl-containing cross-linking agent used, triethyleneglycol divinyl ether, (i.e. two per molecule) is provided as ratio D. For each polymerizable composition, the relative unit parts, based on weight, are shown. Molar percentages (mol. %) and weight percentages (wt. %) for each reactive ingredient are provided, except that mol. % values of less than 0.01 are not provided. The mol. % and wt. % of a given component are relative to the total moles and weight, respectively, of all reactive components in the composition prior to initiation of curing.

TABLE 1 Abbreviation Compound Molecular Wt Si-1 Formula I above wherein R¹ is a butyl group, R² is 583 hydrogen, R³ is a methyl group, m = 4, and n = 1 Si-2 A compound of formula II above wherein R₁ and R₂ are 9,300 methyl groups, m is 0, n represents an integer from about 5 to about 10, a represents an integer of from about 70 to about 90, and b represent an integer of from 1 to about 10 Si-3 Methacryloxypropyl terminated polydimethylsiloxane 4,500 AE 2-Allyloxy ethanol 102 BVE 4-butanediol vinyl ether 116 DEGVE diethylene glycol vinyl ether 132 EGDMA ethylene glycol dimethacrylate 198 EGMA ethylene glycol methyl ether methacrylate 144 EGVE ethylene glycol vinyl ether 88 HEMA 2-hydroxyethyl methacrylate 130 HOB 2-hydroxybutyl methacrylate 158 MMA methyl methacrylate 100 UV2 2-(3-(2H-benzotriazol-2-YL)-4-hydroxy-phenyl) ethyl 323 methacrylate (CAS no. 96478-0-0) pTPP Diphenyl (P-vinylphenyl)phosphine (CAS no. 40538-11-2) 288 RBT1 2-Propenoic acid,2-methyl-,1,1′-[(9,10-dihydro-9,10- dioxo-1,4-anthracenediyl)bis(imino-2,1-ethanediyl)]ester (CAS no. 121888-69-5) RBT2 1,4-bis[4-[(2-methacryl-oxyethyl)phenylamino] anthraquinone TEGDMA triethylene glycol dimethacrylate 286 TEGDVE triethyleneglycol divinyl ether 202 TPP Triphenyl phosphine (CAS no. 603-35-0) V-64 2,2′-Azobis-2-methyl propanenitrile VMA N-vinyl-N-methylacetamide 99

Example 1 Silicone Hydrogel Contact Lens Fabrication

The chemical compounds listed in the tables in Examples 2-12 were weighed and mixed together to form polymerizable compositions. Each polymerizable composition was filtered using a 0.2-5.0 micron filter and stored for up to about 2 weeks at 2-10° C. prior to cast molding and curing.

The polymerizable composition was cast molded by placing a volume of the composition on a female mold member and fitting a male mold member thereon to form a contact lens mold assembly. The female and male mold members were made from a non-polar resin (e.g.polypropylene). The polymerizable composition was thermally cured to form a polymeric lens body by placing the mold assembly in a nitrogen oven at the following cycle: 30 min. N₂ purging at room temperature, 40 min. at 55° or 65° C., 40 min. at 80° C., and 40 min. at 100 ° C.

After curing, the male and female mold members were dry demolded and the polymeric lens bodies were dry delensed from the male mold members. The delensed lens bodies were then extracted in alcohol, followed by hydration in water (Example 2) or were washed using organic-solvent free extraction (Examples 3-12). For alcohol extraction, lens trays containing the polymeric lens bodies were immersed in ethanol. After a period of time the ethanol was exchanged with fresh ethanol. Then the lens bodies were immersed in a solution of 50:50 ethanol/DI water. After a period of time, the lens bodies were immersed in a two exchanges of DI water. For organic solvent-free extraction, lenses were transferred to individual wells of a washing tray containing DI water and Tween 80 (washing solution). After several minutes, the washing solution was aspirated, and the wells refilled with washing solution; this step was repeated 1-2 times. The extracted and hydrated lenses were placed into blister packages containing a buffered packaging solution, and the packages were sealed and autoclaved.

Example 2 Formulation 1

The polymerizable composition of Formulation 1 shown in Table 2 was used to make contact lenses using the methods described in Example 1, in which alcohol extraction was used. The composition had the following approximate molar ratios: A=9:1, B=48:1, C=n/a, and D=504:1.

TABLE 2 Abbreviation Unit Amount Mol. % Wt. % Si-1 30 6.8 26.5 Si-2 10 0.14 8.8 VMA 48 63.9 42.3 EGMA 7 6.4 6.2 MMA 15 19.8 13.2 EGDMA 0.5 0.33 0.44 TEGDVE 0.1 0.07 0.09 AE 1.4 1.8 1.2 V-64 0.5 0.40 0.44 UV2 0.9 0.37 0.79 RBT2 0.01 0.01 TPP 0.5

Silicon hydrogel contact lenses made from this formulation had acceptable dimensional stability, an oxygen permeability of greater than 60 barrers, an EWC of about 53%, a modulus of about 0.40 MPa, a tensile strength of about 1.4 MPa, a dynamic captive bubble advancing contact angle of about 48 to 52 degrees, a light transmittance of about 98%, a wet extractable component of about 1.30%, an ionoflux of about 2.9×10⁻³ mm²/min, and an energy loss from about 35 to 36%.

Example 3 Formulation 2

The polymerizable composition designated Formulation 2 shown in Table 3 was used to make contact lenses using the methods described in Example 1, in which all liquids used for washing the polymeric lens body were substantially free of volatile organic solvents. The composition had the following approximate molar ratios: A=9:1, B=62:1, C=17:1, and D=244:1.

TABLE 3 Abbreviation Unit Amount Mol. % Wt. % Si-1 32 7.9 30.9 Si-3 4 0.13 3.9 VMA 45 64.0 43.5 MMA 13 18.6 12.6 EGMA 3 3.0 2.9 BVE 3 3.7 2.9 TEGDMA 1 0.50 0.97 TEGDVE 0.2 0.14 0.19 pTPP 0.5 0.25 0.48 V-64 0.5 0.43 0.48 RBT1 0.01 0.01 UV2 1.3 0.40 1.3

Silicone hydrogel contact lenses made from this formulation had an EWC of about 57%, a modulus of about 0.70 MPa, an energy loss of about 40%, and a captive bubble dynamic advancing contact angle of from about 50 to about 60 degrees.

Example 4 Formulation 3

The polymerizable composition designated Formulation 3 shown in Table 4 was used to make contact lenses using the methods described in Example 1, in which all liquids used for washing the polymeric lens body were substantially free of volatile organic solvents. The composition had the following approximate molar ratios: A=10:1, B=41:1, C=7:1, and D=236:1.

TABLE 4 Abbreviation Unit Amount Mol. % Wt. % Si-1 26 6.6 25.1 Si-2 10 0.16 9.6 VMA 40 59.5 38.6 MMA 12 17.7 11.6 EGMA 5 5.1 4.8 BVE 7 8.9 6.8 TEGDMA 1.2 0.62 1.2 TEGDVE 0.2 0.15 0.19 pTPP 0.5 0.28 0.48 Vazo64 0.5 0.45 0.48 RB 247 0.01 0.01 UV2 1.3 0.59 1.3

Silicone hydrogel contact lenses made from this formulation had an EWC of about 56%, a modulus of about 0.50 MPa, and a captive bubble dynamic advancing contact angle of about 47 to about 51 degrees.

Example 5 Formulation 4

The polymerizable composition designated Formulation 4 shown in Table 5 was used to make contact lenses using the methods described in Example 1, in which all liquids used for washing the polymeric lens body were substantially free of volatile organic solvents. The composition had the following approximate molar ratios: A=9:1, B=41:1, C=16:1, and D=436:1.

TABLE 5 Abbreviation Unit Amount Mol. % Wt. % Si-1 26 7.0 26.3 Si-2 10 0.17 10.1 VMA 40 62.9 40.4 MMA 12 18.7 12.1 EGMA 5 5.4 5.1 BVE 3 4.0 3.0 EGDMA 0.5 0.39 0.51 TEGDVE 0.1 0.08 0.10 pTPP 0.5 0.27 0.51 V-64 0.5 0.47 1.3 UV2 1.3 0.63 0.01 RBT1 0.01 0.51

Silicone hydrogel contact lenses made from this formulation had an EWC of about 55%, a modulus of about 0.60 MPa, and a captive bubble dynamic advancing contact angle of from about 47 to about 55 degrees.

Example 6 Formulation 5

The polymerizable composition designated Formulation 5 shown in Table 6 was used to make contact lenses using the methods described in Example 1, in which all liquids used for washing the polymeric lens body were substantially free of volatile organic solvents. The composition had the following approximate molar ratios: A=10:1, B=56:1, C=8:1, and D=301:1.

TABLE 6 Abbreviation Unit Amount Mol. % Wt. % Si-1 29 7.1 28.3 Si-2 8 0.12 7.8 VMA 44 63.3 42.9 MMA 14 19.9 13.7 EGVE 5 8.1 4.9 EGDMA 0.6 0.43 0.59 TEGDVE 0.15 0.11 0.15 V-64 0.5 0.43 0.49 UV2 1.3 0.57 1.3 RBT1 0.01 0.01

Silicone hydrogel contact lenses made from this formulation had an EWC of about 56%, and a modulus of about 0.65 MPa.

Example 7 Formulation 6

The polymerizable composition designated Formulation 6 shown in Table 7 was used to make contact lenses using the methods described in Example 1, in which all liquids used for washing the polymeric lens body were substantially free of volatile organic solvents. The composition had the following approximate molar ratios: A=9:1, B=58:1, C=n/a, and D=464:1.

TABLE 7 Abbreviation Unit Amount Mol. % Wt. % Si-1 29 7.3 28.3 Si-2 8 0.13 7.8 VMA 45 66.7 43.9 MMA 13 19.1 12.7 HEMA 4 4.5 3.9 EGDMA 0.5 0.37 0.49 TEGDVE 0.1 0.07 0.10 pTPP 0.5 0.25 0.49 AE 0.3 0.43 1.7 V-64 0.5 0.45 0.01 UV2 1.7 0.77 0.49 RBT1 0.01 0.29

Silicone hydrogel contact lenses made from this formulation had an EWC of from about 55% to about 56%, a modulus of about 0.53 MPa, a captive bubble dynamic advancing contact angle of from about 51 to about 53 degrees, and an energy loss of about 34%.

Example 8 Formulation 7

The polymerizable composition designated Formulation 7 shown in Table 8 was used to make contact lenses using the methods described in Example 1, in which all liquids used for washing the polymeric lens body were substantially free of volatile organic solvents. The composition had the following approximate molar ratios: A=10:1, B=58:1, C=8:1, and D=488:1.

TABLE 8 Abbreviation Unit Amount Mol. % Wt. % Si-1 29 7.5 27.9 Si-2 8 0.13 7.7 VMA 42 63.6 40.5 MMA 8 12.0 7.7 EGMA 6 6.3 5.8 DEGVE 7 8.0 6.7 EGDMA 0.6 0.45 0.58 TEGDVE 0.1 0.07 0.10 pTPP 0.5 0.26 0.48 AE 0.4 0.59 0.39 V-64 0.5 0.46 0.48 UV2 1.7 0.79 1.6 RBT1 0.01 0.01

Silicone hydrogel contact lenses made from this formulation had an EWC of from 57% to 58%, a modulus of about 0.7 MPa, a tensile strength of about 1.5 MPa, a captive bubble dynamic advancing contact angle of from about 44 to about 48 degrees, a wet extractable component of about 5.1%, an ionoflux of about 2.9×10⁻³ mm²/min, and an energy loss from about 32% to about 33%.

Example 9 Formulation 8

The polymerizable composition designated Formulation 8 shown in Table 9 was used to make contact lenses using the methods described in Example 1, in which all liquids used for washing the polymeric lens body were substantially free of volatile organic solvents. The composition had the following approximate molar ratios: A=9:1, B=58:1, C=n/a, and D=464:1.

TABLE 9 Abbreviation Unit Amount Mol. % Wt. % Si-1 29 7.83 28.3 Si-2 8 0.14 7.8 VMA 45 71.6 43.9 HOB 7 7.0 6.8 EGMA 10 10.9 9.8 EGDMA 0.5 0.4 0.49 TEGDVE 0.1 0.08 0.10 pTPP 0.5 0.27 0.49 AE 0.3 0.46 0.29 V-64 0.5 0.48 0.49 UV2 1.7 0.83 1.7 RBT1 0.01 0.01

Silicone hydrogel contact lenses made from this formulation had an EWC of from about 55% to about 56%, a modulus of about 0.6 MPa, a tensile strength of about 1.2 MPa, a captive bubble dynamic advancing contact angle of from about 55 to about 58 degrees, a wet extractable component of about 4.6%, an ionoflux of about 4.1×10⁻³ mm²/min, and an energy loss of from about 31% to about 32%.

Example 10 Formulation 9

The polymerizable composition designated Formulation 9 shown in Table 10 was used to make contact lenses using the methods described in Example 1, in which all liquids used for washing the polymeric lens body were substantially free of volatile organic solvents. The composition had the following approximate molar ratios: A=11:1, B=68:1, C=5:1, and D=752:1.

TABLE 10 Abbreviation Unit Amount Mol. % Wt. % Si-1 30 6.9 26.7 Si-2 7 0.10 6.2 VMA 44 59.9 39.1 MMA 8 10.8 7.1 EGMA 6 5.6 5.3 DEGVE 10 10.2 8.9 BVE 4 4.6 3.6 EGDMA 0.6 0.41 0.53 TEGDVE 0.1 0.05 0.09 pTPP 0.5 0.26 0.44 V-64 0.5 0.41 0.44 RBT1 0.01 0.01 UV2 1.8 0.75 1.6

Silicone hydrogel contact lenses made from this formulation had acceptable dimensional stability, an EWC of about 61%, a modulus of about 0.5 MPa, a tensile strength of about 1.2 MPa, a captive bubble dynamic advancing contact angle of from about 45 to about 47 degrees, a wet extractable component of about 4.55%, an ionoflux of about 3.8×10⁻³ mm²/min, and an energy loss of from about 30% to about 33%.

Example 11 Formulation 10

The polymerizable composition designated Formulation 10 shown in Table 11 was used to make contact lenses using the methods described in Example 1, in which all liquids used for washing the polymeric lens body were substantially free of volatile organic solvents. The composition had the following approximate molar ratios: A=10:1, B=68:1, C=7:1, and D=252:1.

TABLE 11 Abbreviation Unit Amount Mol. % Wt. % Si-1 30 7.07 27.4 Si-2 7 0.10 6.4 VMA 45 62.5 41.1 MMA 12 16.5 11.0 EGMA 6 5.7 5.5 BVE 5 5.9 4.6 TEGDMA 1.4 0.67 1.3 TEGDVE 0.2 0.14 0.18 pTPP 0.5 0.24 0.46 V-64 0.5 0.42 0.46 RBT1 0.01 0.01 UV2 1.8 0.76 1.7

Silicone hydrogel contact lenses made from this formulation had acceptable dimensional stability, an EWC of from about 55% to about 57%, a modulus of about 0.7 MPa, a tensile strength of about 1.3 MPa, a captive bubble dynamic advancing contact angle of from about 47 to about 53 degrees, a wet extractable component of about 4.1%, an ionoflux of about 3.6×10⁻³ mm²/min, and an energy loss of from about 34% to about 35%.

Example 12 Formula 11

The polymerizable composition designated Formulation 11 shown in Table 12 was used to make contact lenses using the methods described in Example 1, in which all liquids used for washing the polymeric lens body were substantially free of volatile organic solvents. The composition had the following approximate molar ratios: A=10:1, B=41:1, C=7:1, and D=457:1.

TABLE 12 Abbreviation Unit Amount Mol. % Wt. % Si-1 25.2 7.04 25.2 Si-2 9.7 0.17 9.7 VMA 38.8 63.9 38.8 BVE 6.8 9.6 6.8 EGMA 4.8 5.4 4.8 EOEMA 11.6 12.0 11.6 TEGDMA 1.2 0.68 1.2 TEGDVE 0.1 0.08 0.10 V-64 0.5 0.50 0.50 UV2 0.9 0.45 0.9 RBT1 0.01 0.01 pTPP 0.5 0.28 0.50

Silicone hydrogel contact lenses made from this formulation had an EWC of about 56%, a modulus of about 0.57 MPa, a tensile strength of about 1.90 MPa, a wet extractable component of about 4.74%, and an energy loss of about 34 to 36%.

Although the disclosure herein refers to certain illustrated examples, it is to be understood that these examples are presented by way of example and not by way of limitation. The intent of the foregoing detailed description, although discussing exemplary examples, is to be construed to cover all modifications, alternatives, and equivalents of the examples as may fall within the spirit and scope of the invention as defined by the additional disclosure.

A number of publications and patents have been cited hereinabove. Each of the cited publications and patents are hereby incorporated by reference in their entireties. 

1. A silicone hydrogel contact lens comprising: a polymeric lens body that is a reaction product of a polymerizable composition comprising a) at least one acrylate-containing siloxane monomer represented by formula (I):

where m is an integer from 3 to 10, n is an integer from 0 to 10, R¹ is an alkyl group having 1 to 4 carbon atoms, R² is hydrogen or a methyl group, and R³ is hydrogen or a methyl group; b) at least one hydrophilic vinyl-containing monomer; and c) at least one vinyl-containing cross-linking agent, wherein the contact lens has an ionoflux of less than 10×10⁻³ mm²/min.
 2. The contact lens of claim 1, wherein the polymerizable composition has a total amount of acrylate-containing siloxane monomer of from about 2 mol. % to about 15 mol. %.
 3. The contact lens of claim 1, wherein the polymerizable composition has a total amount of hydrophilic vinyl-containing monomer of from about 50 mol. % to about 85 mol. %.
 4. The contact lens of claim 1, wherein the polymerizable composition has a total amount vinyl-containing cross-linking agent of from about 0.02 mol. % to about 0.20 mol. %.
 5. The contact lens of claim 1, wherein the polymerizable composition has a molar ratio of total amount of hydrophilic vinyl-containing monomer to total amount of acrylate-containing siloxane monomer of from 5:1 to 30:1, respectively.
 6. The contact lens of claim 1, wherein the at least one hydrophilic vinyl-containing monomer is selected from N-vinyl-N-methyl acetamide (VMA), or N-vinyl pyrrolidone (NVP), or 1,4-butanediol vinyl ether (BVE), or ethylene glycol vinyl ether (EGVE), or diethylene glycol vinyl ether (DEGVE), or any combination thereof.
 7. The contact lens of claim 1, wherein the at least one hydrophilic vinyl-containing monomer is N-vinyl-N-methyl acetamide (VMA).
 8. The contact lens of claim 1, wherein the at least one hydrophilic vinyl-containing monomer comprises a first hydrophilic vinyl-containing monomer having a first polymerizable group and a second hydrophilic vinyl-containing monomer having a second polymerizable group that is different from the first polymerizable group.
 9. The contact lens of claim 1, wherein the at least one hydrophilic vinyl-containing monomer comprises at least one hydrophilic vinyl amide-containing monomer and at least one hydrophilic vinyl ether-containing monomer.
 10. The contact lens of claim 9, wherein the polymerizable composition has a molar ratio of total amount of hydrophilic vinyl amide-containing monomer to total amount of hydrophilic vinyl ether-containing monomer of from 2:1 to 30:1, respectively.
 11. The contact lens of claim 9, wherein the polymerizable composition has a molar ratio of total amount of hydrophilic vinyl amide-containing monomer to total amount of hydrophilic vinyl ether-containing monomer of from 4:1 to 15:1, respectively.
 12. The contact lens of claim 9, wherein the polymerizable composition has a total amount of vinyl amide-containing monomer of from about 50 to about 75 mol. %.
 13. The contact lens claim 9, wherein the polymerizable composition has a total amount vinyl ether-containing monomer of from about 2 to about 20 mol. %.
 14. The contact lens of claim 1, wherein the at least one vinyl-containing cross-linking agent is selected from divinyl ether, or divinyl sulfone, or triallyl phthalate, or triallyl isocyanurate, or diallyl phthalate, or diethyleneglycol divinyl ether, or triethyleneglycol divinyl ether, or any combination thereof.
 15. The contact lens of claim 1, wherein the at least one vinyl-containing cross-linking agent is a divinyl ether.
 16. The contact lens of claim 1, further comprising a bi-functional acrylate-containing siloxane monomer.
 17. The contact lens of claim 16, wherein the bi-functional acrylate-containing siloxane monomer has a molecular weight of at least 3,000.
 18. The contact lens of claim 16, wherein the acrylate-containing siloxane monomer represented by formula (I) and the bi-functional acrylate-containing siloxane monomer are present in the polymerizable composition at a molar ratio of at least 30:1, respectively.
 19. The contact lens of claim 1, wherein the polymerizable composition further comprises at least one non-siloxane acrylate-containing monomer.
 20. The contact lens of claim 1, wherein the polymerizable composition has a total amount of cross-linkable ingredients of from about 0.2 to about 1.5 mol. %.
 21. The contact lens of claim 1 having an ionoflux of less than 8×10⁻³ mm²/min.
 22. The contact lens of claim 1, wherein the polymerizable composition is substantially free of hydrophilic polymer.
 23. The contact lens of claim 1 that is free of post-polymerization surface modification.
 24. The contact lens of claim 1 characterized by one or more of the following features: a) a dynamic advancing contact angle of less than 70° as determined using a captive bubble method; b) an oxygen permeability of at least 60 barrers; c) a tensile modulus from about 0.2 MPa to about 0.9 MPa; d) an equilibrium water content from about 30% wt/wt to about 70% wt/wt; e) an energy loss from about 27 to about 45%; and f) an ionoflux of less than 6×10⁻³ mm²/min.
 25. The contact lens of claim 1 having a wet extractable component of about 2 to about 8% based on dry weight of the contact lens.
 26. The contact lens of claim 1 sterilized in a sealed package.
 27. A method of manufacturing the silicone hydrogel contact lens of claim 1 comprising: polymerizing the polymerizable composition to make the polymeric lens body, and washing the polymeric lens body with a washing liquid to remove unreacted or partially reacted components from the polymeric lens body.
 28. The method of claim 27, wherein the washing liquid and any other liquid used for washing the polymeric lens body are substantially free of volatile organic solvents.
 29. A method of manufacturing a silicone hydrogel contact lens comprising: a) preparing a polymerizable composition comprising at least one acrylate-containing siloxane monomer represented by formula (I):

at least one hydrophilic vinyl-containing monomer, and at least one vinyl-containing cross-linking agent; b) polymerizing the polymerizable composition to form a polymeric lens body; and c) contacting the polymeric lens body with a washing liquid to remove unreacted or partially reacted components from the polymeric lens body, wherein the washing liquid and any other liquid used for washing the polymeric lens body are substantially free of volatile organic solvents.
 30. The method of claim 29, further comprising sealing the polymeric lens body in a package comprising a packaging solution and sterilizing the sealed package.
 31. The method of claim 29, wherein the polymerizing occurs in a mold having non-polar molding surfaces.
 32. The method of any one of claim 29, wherein the polymerizing step comprises thermal curing.
 33. The method of claim 32, wherein the polymerizing step comprises a first curing temperature of about 50 to 65° C. maintained for about 15 to 45 minutes, and a second curing temperature of at least about 70° C.
 34. The method of claim 33, wherein the second curing temperature is about 70 to 85° C. and is maintained for about 15 to 45 minutes, and the thermal curing process further comprises a third curing temperature of at least about 90° C. maintained for at least about 15 minutes.
 35. The method of claim 29 that is free of a post-polymerization surface modification step. 